WO2013135700A1 - Procédé de production d'un gaz de synthèse - Google Patents

Procédé de production d'un gaz de synthèse Download PDF

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Publication number
WO2013135700A1
WO2013135700A1 PCT/EP2013/055005 EP2013055005W WO2013135700A1 WO 2013135700 A1 WO2013135700 A1 WO 2013135700A1 EP 2013055005 W EP2013055005 W EP 2013055005W WO 2013135700 A1 WO2013135700 A1 WO 2013135700A1
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WO
WIPO (PCT)
Prior art keywords
heating
group
threshold value
reactor
fluid
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PCT/EP2013/055005
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German (de)
English (en)
Inventor
Alexander Karpenko
Oliver Felix-Karl SCHLÜTER
Thomas Westermann
Emanuel Kockrick
Albert TULKE
Daniel Duff
Stefanie Eiden
Kristian VOELSKOW
Vanessa GEPERT
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Bayer Intellectual Property Gmbh
Bayer Technology Services Gmbh
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Publication of WO2013135700A1 publication Critical patent/WO2013135700A1/fr

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    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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Definitions

  • the present invention relates to a process for the production of synthesis gas, comprising the steps of providing a flow reactor, setting thresholds, comparing energy prices and / or other operating parameters for the reactor and, in summary, operating between dry reforming and reverse water gas modes. shift reaction.
  • synthesis gas is produced by steam reforming of methane. Due to the high heat demand of the reactions involved, they are carried out in externally heated reformer tubes. Characteristic of this method is the limitation by the reaction equilibrium, a heat transport tempering and, above all, the pressure and temperature limitation of the reformer tubes used (nickel-based steels). Temperature and pressure side results in a limitation to a maximum of 900 ° C at about 20 to 40 bar.
  • DE 10 2007 022 723 A1 and US 2010/0305221 describe a process for the production and conversion of synthesis gas, which is characterized in that it has a plurality of different operating states, which essentially consist of the alternating (i) daytime operation and (ii) night operation, wherein daytime operation (i) mainly comprises dry reforming and steam reforming with the supply of regenerative energy and night operation (ii) mainly the partial oxidation of hydrocarbons and wherein the produced synthesis gas is used to produce value products.
  • US 2007/003478 Al discloses the production of synthesis gas with a combination of steam reforming and oxidation chemistry. The process involves the use of solids to heat the hydrocarbon feed and to cool the gaseous product. According to this publication, heat can be conserved by reversing the gas flow of feed and product gases at intervals.
  • WO 2007/042279 AI deals with a reformer system with a reformer for the chemical reaction of a hydrocarbon-containing fuel in a hydrogen gas-rich reformate gas, and electric heating means by which the reformer heat energy for producing a reaction temperature required for the feed can be supplied, wherein the reformer system further comprises a capacitor has, which can supply the electric heating means with electric current.
  • WO 2004/071947 A2 / US 2006/0207178 AI relate to a system for the production of hydrogen, comprising a reformer for generating hydrogen from a hydrocarbon fuel, a compressor for compressing the generated hydrogen, a renewable energy source for converting a renewable resource into electrical Energy for driving the compressor and a storage device for storing the hydrogen from the compressor.
  • the goal is the use of electrical energy for the continuous production of synthesis gas.
  • C02 should preferably be used as part of the educt stream (but not limited to CO 2 only).
  • high temperatures »850 ° C are desirable in order to maximize yields.
  • the synthesis gas produced thereby can be used for the production of synthetic oil by the Fischer-Tropsch reaction.
  • Associated Gas Parallel to each oil extraction occurs as a minor component so-called "Associated Gas", which is dissolved under high pressure in the Earth's interior in the oil. Since there are few opportunities for the use of "Associated gas” in the case of oil fields on the open sea, this is usually completely (catalytically and homogeneously) burned in turbines, flared or pumped back into the oil field. In the case of combustion, no chemical value-added products are produced and only C02 and H20 are produced. Additional energy is needed for pumping, which adds to the overall product cost.
  • An alternative for the utilization of "Associated gas” is the so-called gas-to-liquid process. "Associated gas” can be converted into synthesis gas by steam reforming.
  • a H2 and CO mixture is produced in the ratio 3: 1. Due to the thermodynamic limitation of the reforming, 10 to 20% of the total methane (depends on the initial temperature and pressure) remains unreacted. Therefore, an alternative is sought to improve the overall efficiency of the reforming process.
  • the Fischer-Tropsch reaction produces a liquid phase as a mixture of hydrocarbons with chain lengths greater than 5 (C5 +, synthetic oil). The excess hydrogen can be separated from the synthesis gas and needs a recovery, which is based on an oil Platform or a ship is not given (no further use within a chemical production chain possible). Additionally arise C1-C4 gaseous products and unreacted CO / H 2 mixture, which also require use.
  • the object of the present invention has been made to make the process of endothermic and / or exothermic synthesis gas generation in terms of energy requirements so that the conversion of methane in the reforming process improved and parallel to excess hydrogen, C 1 -C 4 gaseous hydrocarbons and the remaining CO / H 2 Mixture of the Fischer-Tropsch reaction can be used economically and ecologically.
  • the final product in this case synthetic oil / C5 + production is only intermediate
  • optimally optimally (more economically, ecologically speaking, better carbon efficiency for the entire process) can be produced.
  • a continuous Syngasher ein (production assurance) should be ensured.
  • a process for the production of synthesis gas comprising the steps of: providing a flow reactor, which is adapted to react a fluid comprising reactants, wherein the reactor comprises at least one heating level, which is electrically heated by means of one or more heating elements, wherein the heating level can be traversed by the heating level and wherein at least one catalyst is arranged and can be heated there;
  • Threshold Sl for the cost of available for the flow reactor electrical energy and / or a
  • Threshold S2 for the flow reactor available amount of electrical energy and / or a
  • Heating elements 110, 111, 112, 113, if at least one of the criteria applies: the threshold value Sl is exceeded and / or and the threshold value S2 is exceeded and / or the threshold value S3 is exceeded and / or the threshold value S4 is undershot; wherein the reactions (A) and (B) are carried out at a given time in an arbitrary proportion to each other.
  • the first threshold S 1 relates to the electricity costs for the reactor, in particular the costs for an electrical heating of the reactor by the heating elements in the heating levels. Here it can be determined up to which height the electric heating is still economically reasonable.
  • the second threshold value S2 relates to the electrical energy available for the flow reactor and in particular for the heating operation. This parameter is of particular concern when considering stand-alone systems such as ships or oil rigs.
  • the third threshold S3 relates to the production request to the reactor.
  • the fourth threshold S4 represents how many of the generally available hydrocarbons for synthesis gas production and how many are provided for generating electrical energy in an internal combustion engine generator. It is thus an allocation of the chemical energy source in the form of hydrocarbons for chemical reactions or for energy production. This is again particularly relevant for self-sufficient systems such as ships or oil rigs.
  • a comparison of the desired values with the actual values in the method can now reach the conclusion that electrical energy is available at low cost, enough electrical energy is available, more synthesis gas is needed and / or enough hydrocarbons are available. Then the flow reactor is operated so that, for example, a dry reforming reaction takes place.
  • the hydrocarbons involved are preferably alkanes, alkenes, alkynes, alkanols, alkenols and / or alkynols.
  • alkanes methane is particularly suitable, among the alkanols methanol and / or ethanol are preferred.
  • the flow reactor is operated so that, for example, an RWGS reaction takes place.
  • the combustion of hydrogen can be used. It is also possible that the combustion of hydrogen in the RWGS reaction by metering of 0 2 in the educt gas (ideally a locally distributed or lateral addition) takes place, as well as possible that hydrogen-rich residual gases (for example, PSA exhaust gas), as they may be incurred in the purification of the synthesis gas, returned and burned together with 0 2 , which then the process gas is heated.
  • hydrogen-rich residual gases for example, PSA exhaust gas
  • An advantage of the oxidative mode of operation is that soot deposits formed by dry reforming or steam reforming can be removed and thus the catalyst used can be regenerated. Moreover, it is possible to regenerate passivation layers, the heating conductor or other metallic internals in order to increase the service life.
  • endothermic reactions are heated from the outside through the walls of the reaction tubes. Opposite is the autothermal reforming with 0 2 -addition.
  • the endothermic reaction can be efficiently internally supplied with heat via an electrical heating within the reactor (the undesired alternative would be electrical heating via radiation through the reactor wall).
  • the inventive method provides to run the DR, SMR and RWGS reactions in the same reactor.
  • a mixed operation is expressly provided.
  • One of the advantages of this approach is the gradual onset of each other's reaction, for example, by continuously reducing hydrogen supply while increasing the supply of methane, or by continuously increasing hydrogen supply while reducing methane feed.
  • the various threshold values can be weighted so as to find a satisfactory solution for the reactor operation for a multi-dimensional optimization problem.
  • a dynamic mode of operation i.e., flexibility and safety
  • selection between different endothermic and / or exothermic reactions in the post-reactor is possible.
  • FIG. 1 shows schematically a flow reactor in an expanded representation.
  • FIG. 2 schematically shows a production network using the method according to the invention.
  • the flow reactor comprises: seen in the flow direction of the fluid, a plurality of heating levels, which are electrically heated by heating elements and wherein the heating levels are permeable by the fluid, wherein a catalyst is arranged on at least one heating element and is heatable there, wherein further at least once an intermediate plane between two heating levels is arranged and wherein the intermediate plane is also traversed by the fluid.
  • FIG. 1 schematically shown flow reactor used according to the invention is flowed through by a fluid comprising reactants from top to bottom, as shown by the arrows in the drawing.
  • the fluid may be liquid or gaseous and may be single-phase or multi-phase.
  • the fluid is gaseous. It is conceivable that the fluid contains only reactants and reaction products, but also that additionally inert components such as inert gases are present in the fluid.
  • the reactor has a plurality of (four in the present case) heating levels 100, 101, 102, 103, which are electrically heated by means of corresponding heating elements 110, 111, 112, 113.
  • the heating levels 100, 101, 102, 103 are flowed through by the fluid during operation of the reactor and the heating elements 110, 111, 112, 113 are contacted by the fluid.
  • At least one heating element 110, 111, 112, 113, a catalyst is arranged and is heated there.
  • the catalyst may be directly or indirectly connected to the heating elements 110, 111, 112, 113 so that these heating elements constitute the catalyst support or a support for the catalyst support.
  • the heat supply of the reaction takes place electrically and is not introduced from the outside by means of radiation through the walls of the reactor, but directly into the interior of the reaction space. It is realized a direct electrical heating of the catalyst.
  • thermoistor alloys such as FeCr Al alloys are preferably used.
  • electrically conductive Si-based materials particularly preferably SiC.
  • This has the effect of homogenizing the fluid flow.
  • additional catalyst is present in one or more intermediate levels 200, 201, 202 or other isolation elements in the reactor. Then an adiabatic reaction can take place.
  • the intermediate levels may act as flame arresters as needed, especially in reactions where oxygen delivery is provided.
  • the material forms an Al 2 O 3 protective layer by the action of temperature in the presence of air / oxygen.
  • This passivation layer can serve as a basecoat of a washcoat, which acts as a catalytically active coating.
  • the direct resistance heating of the catalyst or the heat supply of the reaction is realized directly through the catalytic structure.
  • the formation of other protective layers such as Si-OC systems.
  • the pressure in the reactor can take place via a pressure-resistant steel jacket.
  • suitable ceramic insulation materials it can be achieved that the pressure-bearing steel is exposed to temperatures of less than 200 ° C and, if necessary, less than 60 ° C.
  • the electrical connections are shown in FIG. 1 only shown very schematically. They can be routed in the cold area of the reactor within an insulation to the ends of the reactor or laterally from the heating elements 110, 111, 112, 113, so that the actual electrical connections can be provided in the cold region of the reactor.
  • the electrical heating is done with direct current or alternating current.
  • heating elements 110, 111, 112, 113 are arranged, which are constructed in a spiral, meandering, grid-shaped and / or reticulated manner.
  • At least one heating element 110, 111, 112, 113 may have a different amount and / or type of catalyst from the other heating elements 110, 111, 112, 113.
  • the heating elements 110, 111, 112, 113 are arranged so that they can each be electrically heated independently of each other.
  • the individual heating levels can be individually controlled and regulated.
  • In the reactor inlet area can be dispensed with a catalyst in the heating levels as needed, so that only the heating and no reaction takes place in the inlet area. This is particularly advantageous in terms of starting the reactor.
  • a temperature profile adapted for the respective reaction can be achieved. With regard to the application for endothermic equilibrium reactions, this is, for example, a temperature profile which achieves the highest temperatures and thus the highest conversion at the reactor outlet.
  • the (for example ceramic) intermediate levels 200, 201, 202 or their contents 210, 211, 212 comprise a material resistant to the reaction conditions, for example a ceramic foam.
  • the material of the content 210, 211, 212 of an intermediate level 200, 201, 202 comprises oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • SiC silicon and / or zirconium.
  • cordierite is an example of this.
  • the intermediate level 200, 201, 202 may include, for example, a loose bed of solids. These solids themselves may be porous or solid, so that the fluid flows through gaps between the solids. It is preferred that the material of the solid bodies comprises oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium. An example of this is SiC. Further preferred is cordierite. It is also possible that the intermediate plane 200, 201, 202 comprises a one-piece porous solid. In this case, the fluid flows through the intermediate plane via the pores of the solid. This is shown in FIG. 1 shown. Preference is given to honeycomb monoliths, as used for example in the exhaust gas purification of internal combustion engines. Another conceivable possibility is that one or more of the intermediate levels are voids.
  • the average length of a heating level 100, 101, 102, 103 is viewed in the direction of flow of the fluid and the average length of an intermediate level 200, 201, 202 in the direction of flow of the fluid is in a ratio of> 0.01: 1 to ⁇ 100: 1 to each other. Even more advantageous are ratios of> 0.1: 1 to ⁇ 10: 1 or 0.5: 1 to ⁇ 5: 1.
  • Suitable catalysts may, for example, be selected from the group comprising:
  • A, A 'and A are independently selected from the group: Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, Sn, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Tl, Lu, Ni, Co, Pb, Bi and / or Cd;
  • B, B 'and B are independently selected from the group: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb , Hf, Zr, Tb, W, Gd, Yb, Mg, Li, Na, K, Ce and / or Zn; and
  • A, A 'and A are independently selected from the group: Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu , Gd, Tb, Dy, Ho, Er, Tm, Yb, Tl, Lu, Ni, Co, Pb and / or Cd;
  • B is selected from the group: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb, Hf, Zr, Tb, W , Gd, Yb, Bi, Mg, Cd, Zn, Re, Ru, Rh, Pd, Os, Ir and / or Pt; B 'is selected from the group: Re, Ru, Rh, Pd, Os, Ir and / or Pt;
  • B is selected from the group: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb, Hf, Zr, Tb, W, Gd, Yb, Bi, Mg, Cd and / or Zn, and 0 ⁇ w ⁇ 0.5, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, and 1 ⁇ delta ⁇ 1;
  • Ml and M2 are independently selected from the group: Re, Ru, Rh, Ir, Os, Pd and / or Pt;
  • M3 is selected from the group: Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu;
  • M is selected from the group: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cu , Ag and / or Au;
  • L is selected from the group: Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, Sn, Pb, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb and / or Lu; and 4 ⁇ z ⁇ 9;
  • a metal Ml and / or at least two different metals Ml and M2 on and / or in a carrier wherein the carrier comprises a carbide, oxycarbide, carbonitride, nitride, boride, silicide, germanide and / or selenide of metals A and / or B is;
  • Ml and M2 are independently selected from the group: Cr, Mn, Fe, Co, Ni, Re, Ru, Rh, Ir, Os, Pd, Pt, Zn, Cu, La, Ce, Pr, Nd, Sm, Eu , Gd, Tb, Dy, Ho, Er, Tm, Yb, and / or Lu;
  • a and B are independently selected from the group: Be, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Hf, Ta, W, La, Ce , Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and / or Lu;
  • (VIII) a catalyst comprising Ni, Co, Fe, Cr, Mn, Zn, Al, Rh, Ru, Pt and / or Pd;
  • reaction products includes the catalyst phases present under reaction conditions.
  • an electric heating of at least one of the heating elements 110, 111, 112, 113 takes place in the reactor provided. This can, but does not have to, take place before the flow of a reactant through the flow reactor under at least partial reaction of the reactants of the fluid.
  • the reactor can be modular.
  • a module may include, for example, a heating level, an insulation level, the electrical contact and the corresponding further insulation materials and thermal insulation materials.
  • the reaction temperature in the reactor is at least in places> 700 ° C to ⁇ 1300 ° C. More preferred ranges are> 800 ° C to ⁇ 1200 ° C and> 900 ° C to ⁇ 1100 ° C.
  • the average (mean) contact time of the fluid to a heating element 110, 111, 112, 113 may be, for example,> 0.01 seconds to ⁇ 1 second and / or the average contact time of the fluid to an intermediate level 110, 111, 112, 113 may be, for example > 0.001 seconds to ⁇ 5 seconds.
  • Preferred contact times are> 0.005 to ⁇ 1 second, more preferably> 0.01 to ⁇ 0.9 seconds.
  • the reaction can be carried out at a pressure of> 1 bar to ⁇ 200 bar.
  • the pressure is> 2 bar to ⁇ 50 bar, more preferably> 10 bar to ⁇ 30 bar.
  • At least some of the fluids reacting in the flow reactor originate from an upstream reforming process for hydrocarbons.
  • the reactor described here is to be understood as a post-reformer.
  • this further comprises the step of Fischer-Tropsch synthesis with the synthesis gas obtained.
  • FIG. 2 Such a composite with the reactor in which the method according to the invention is carried out is shown in FIG. 2 shown.
  • an operating phase due to high demand for syngas for increased FT production and / or high supply of electrical energy (eg through overproduction of hydrogen in the SMR reformer and / or high proportion of C1-C4, hydrogen and / or tail gas "), even more synthesis gas is produced in the optimal H 2 : CO ratio with the help of energy-intensive dry reforming
  • the process of syngas production is switched to the less energy-intensive RWGS (by the addition of the C02 / H 2 mixture.)
  • the process described above in the post-reformer (secondary reactor) with high outlet temperatures and for the C0 2 use (as part of the Eduktsstoms) for the synthetic oil production is carried out in an electrically heatable reactor, which can be used for all the above-mentioned reaction.
  • the reformer described above can take over in the case of failure of SMR reformer, the production of the syngas partially or completely.
  • the device according to the invention enables the separation / recovery of hydrogen and Kohlenmooxides from synthesis gas.
  • At least a portion of the syngas may be used for the Fischer-Tropsch synthesis, and a portion of the hydrogen, C1-C4 and / or tail gas may be used to generate electrical energy by combustion in turbines and their use for heating the post-reactor ( At least part of the synthetic oil is mixed with mineral oil, whereby at least part of the synthetic oil can be used as diesel, gasoline and / or kerosene (jet fuels) the further processing / separation can be used.
  • the present invention relates to a control unit which is set up for the control of the method according to the invention.
  • This control unit can also work on several Modules that communicate with each other, distributed or then include these modules.
  • the controller may include a volatile and / or non-volatile memory containing machine-executable instructions associated with the method of the invention. In particular, these may be machine-executable instructions for detecting the threshold values, for comparing the threshold values with the currently prevailing conditions and for controlling control valves and compressors for gaseous reactants.

Abstract

L'invention concerne un procédé comprenant les étapes qui consistent à fournir un réacteur à écoulement conçu pour faire réagir un fluide renfermant des matières de départ; établir plusieurs valeurs de seuil; et comparer ces valeurs de seuil avec les conditions régnant à ce moment-là dans le réacteur. En fonction de la comparaison des valeurs de seuil, il est possible de réaliser différentes opérations telles qu'un reformage à sec, des réactions de conversion à la vapeur d'eau ou des mélanges de ces réactions dans le réacteur.
PCT/EP2013/055005 2012-03-13 2013-03-12 Procédé de production d'un gaz de synthèse WO2013135700A1 (fr)

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PCT/EP2013/055010 WO2013135705A1 (fr) 2012-03-13 2013-03-12 Procédé pour produire du co et/ou h2 en fonctionnement alterné entre deux types de fonctionnement
PCT/EP2013/055017 WO2013135710A2 (fr) 2012-03-13 2013-03-12 Procédé pour la réalisation d'une réaction rwgs dans un réacteur à faisceau tubulaire
PCT/EP2013/055012 WO2013135707A1 (fr) 2012-03-13 2013-03-12 Procédé pour produire un mélange gazeux contenant du monoxyde de carbone à des températures élevées sur des catalyseurs à base d'oxyde de mischmétal renfermant des métaux nobles
PCT/EP2013/055005 WO2013135700A1 (fr) 2012-03-13 2013-03-12 Procédé de production d'un gaz de synthèse
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PCT/EP2013/055017 WO2013135710A2 (fr) 2012-03-13 2013-03-12 Procédé pour la réalisation d'une réaction rwgs dans un réacteur à faisceau tubulaire
PCT/EP2013/055012 WO2013135707A1 (fr) 2012-03-13 2013-03-12 Procédé pour produire un mélange gazeux contenant du monoxyde de carbone à des températures élevées sur des catalyseurs à base d'oxyde de mischmétal renfermant des métaux nobles

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